ChE 391: Chemical Engineering Laboratory I

Title of Experiment (Experiment No. 8) (Sequence No. 3)

Date of Experiment: If make-up, state reasons:

19/01/2012 -

(Regular/Make-up)

Regular

Date of Report Submission: 02/02/2012 (Any revision sought: Yes/No If yes, state reasons for make-up:

(Regular/Make-up)

Regular

Group No.: Batch: 1. Smriti Agrawal 2. Mounica Bodapudi 3. Lavanya 4. Nidhi Rajwania

6 Thursday Y9587 Y9175 Y9368 Y9306

Name of TA:

Shilpi Saxena

Marks: ______________

I/C Prof. P. K. Bhattacharya Dr. Sri Sivakumar

Department of Chemical Engineering Indian Institute of Technology Kanpur

Content
1. 2. 3. 4. 5. 6. 7. 8. 9.

Page no.
3 3 3 3 6 7 8 11 11

Introduction Objective Theory Keywords Procedure Observation Calculation Discussion Error analysis

Continuous Stirred Tank Reactor

Introduction
In a continuous-flow stirred-tank reactor (CSTR), reactants and products are continuously added and withdrawn. The low driving force makes possible better control of rapid exothermic and endothermic reactions. Analysis of a CSTR helps in determining the kinetics of a chemical reaction, i.e. rate law of the reaction. Depending on the conversion, selectivity and yield required, various reaction variables such as temperature, concentration of the reactants etc. can be controlled with the proper knowledge of the rate law. The CSTR configuration is widely used in industrial applications and in wastewater treatment units (i.e. activated sludge reactors).

OBJECTIVE
To determine the reaction rate of the saponification reaction at ambient conditions and determine the reaction rate constant for it To verify the order of the reaction

Keywords
CSTR, reaction rate constant, order of reaction

Relevant Reaction
NaOH + CH3COOC2H5 CH3COONa + C2H5OH

Theory and Formulae

Residence time is expressed as and =VR/VO, min, where VR = Reactor volume (volume of fluid in the reactor), in litres, and VO =Volumetric feed rate (Feed rate of Reactant A + Reactant B), in LPM. The design equation for the mixed flow reactor at steady state is: =VR/VO = CAO*XA/ (-rA) = (CAO- CA)/ (-rA) XA and rA are evaluated at exit stream conditions, which are the same as the conditions within the reactor in a perfectly mixed CSTR. [1]
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For a second order reaction: A+B C+D

With CAO = CBO and under constant volume condition rate (for a second order reaction) can be represented as -rA = -dCA/dt = KCA2 =VR/VO = CAO*XA/ (-rA) = (CAO- CA)/ (-rA) =(CAO- CA)/ KCA2 (1) Degree of conversion, XA = (CAO- CA)/CAO (2) and rate of reaction, -rA = CAO*XA/ , g mol/ L min (3) the rate constant, K = (CAO- CA)/ CA2, L/g mol min (4) For nth order reaction, -rA =K CAn log(-rA) = log K + n*logCA The order of the reaction, n, can be obtained from a plot of log (rA) vs. log CA, that yields a straight line with slope = n, and intercept (at CA = 1 or at log CA = 0) shall give the value of log(K). Also, a plot of vs. XA/(1-XA)2 shall yield a straight line for an assumed second order reaction with slope = 1/(KCAO). From this slope, rate constant K can be obtained. [2]

APPARATUS REQUIRED
1) Electricity supply: single phase, 220 VAC, 50 Hz, 5-15 Amp socket with earth connection 2) Distilled water (to prepare solution) 3) Drain required 4) 5 conical flasks 5) Measuring cylinder 6) 2 stopwatches 7) Burette

8)

Chemicals: NaOH pellets N/10 HCl Ethyl acetate Indicator(phenolphthalein)

Quantity: 100 g 100 ml 200 ml few drops

DESCRIPTION OF THE EXPERIMENTAL SET UP The set-up has two sump tanks to which the NaOH and CH3COOC2H5 solutions are fed. The reactant solutions from these sump tanks are pumped to two overhead storage tanks. The reactants are supplied to the CSTR from these storage tanks and their flow rates are controlled by Rotameters. There is a stirrer in the CSTR for proper mixing. Samples for analysis are collected from the top outlet of the CSTR. The samples are analyzed by titration with NaOH solution. The simplified flow sheet for the experimental set up is :

EXPERIMENTAL PROCEDURE
1) Firstly, the reactant solutions to be used for the experiment were prepared. 20 L of 0.1N NaOH solution by dissolving 80gm NaOH in 20L water and 20 L of 0.1N CH3COOC2H5 solution by mixing 200.24 ml CH3COOC2H5 in 20L water. 2) The respective tanks were filled with these solutions and the motor was switched on to fill them into their respective overhead tanks. 3) Equal volumetric flow rates of both NaOH and CH3COOC2H5 were fed into the CSTR. The flow rates of the streams were measured with the Rotameter. 4) When the liquid in the reactor reached a certain level (nearly 3/4th) it started overflowing and the volume of liquid inside it became constant. It was at this instance that the stirrer of the CSTR was switched on. 5) Next, the heater, provided on the set-up, was switched on and a desired temperature was set on its digital controller. 6) An experimental measurement of the flow rate was made by collecting the product stream in a measuring cylinder for a certain time period, measured on a stopwatch. This flow rate was used to make an estimate of the residence time for the reactor. 7) Once the desired temperature was reached, it was assured that the reactor had reached steady state by allowing it to run undisturbed for 10 minutes or the calculated residence time, whichever was greater.

8) A 10ml sample of the product was taken from the outlet of the CSTR and was added to20ml 0.1N HCl kept in a flask. 9) The solution left in the flask was titrated with 0.1N NaOH which was added drop by drop from a burette, using phenolphthalein as indicator. The volume of NaOH (VNaOH) required for the complete neutralization of the leftover HCl was noted. 10) The steps 3 to 9 were repeated for different values of temperatures and different flow rates for each value of temperature. 11)The experiment was conducted at 40,50 and 600oC and the flow rates used for each temperature were 7.5,12.5 and 15 LPH, as measured by the Rotameter.

Observations:
T=16 oC
Rotamet er reading 7.5 Volume in ml 57 Time in Flow s rate in l/min 14.44 0.24 t,Reside nce time in min 9.08 Initia Final l NaO NaOH H 41 58 63 55.4 3.0 20.0 37.0 55.0 72.5 1.0 18.0 58 75.2 80 72.4 19.5 36.5 55.0 72.5 89.5 18.0 35.3 Differe nce 17 17.2 17 17 16.5 16.5 18.0 17.5 17.0 17.0 17.3

10.0 12.5

37 44

6.10 5.72

0.36 0.461 5

5.9 5.41

T=28 oC
Rotamet er Volume in ml Time in Flow s rate t, Residen Initia l Final NaO Differe nce

reading 7.5 35 7.40

in l/min 0.28

ce time in min 7.58

NaOH H 35.3 53.2 2.0 19.8 37.8 55.8 3.0 21.2 39.4 57.2 16.2 34.0 53.2 71.0 19.8 37.8 55.8 74.2 21.2 39.4 57.2 75.0 34.0 52.0 17.9 17.8 17.8 18.0 18.0 18.4 18.2 18.2 17.8 17.8 17.8 18.0

10.0

47

7.00

0.40

5.33

12.5

51

6.37

0.48

4.47

T=38 oC
Rotamet er reading 7.5 Volume in ml 79 Time in Flow s rate in l/min 18.87 0.25 t,Reside nce time in min 8.56 Initia Final l NaO NaOH H 52.0 20.0 38.2 58.0 22.0 55.8 74.6 30.0 14.0 32.0 51.0 69.0 70.6 38.2 56.8 76.8 38.8 74.6 93.6 49.0 32.0 51.0 69.0 87.4 Differe nce 18.6 18.2 18.6 18.8 18.8 18.8 19.0 19.0 18.0 19.0 18.0 18.4

10.0

48

7.56

0.38

5.64

12.5

39

5.56

0.42

5.12

SAMPLE CALCULATION
T= 150C
Flow rate = 7.5 LPH

Outlet Volumetric Flow Rate = 57 ml / 14.44 sec = 14.210 LPH Residence Time = 2.15 li / 14.210 LPH = 9.078 min Volume of HCl added = 20ml Moles of HCl added = 20ml X 0.1006M = 2.012 mMol NaOH from the burette consumed = 17.0 ml Moles of NaOH consumed = 17.0ml X 0.1016M = 1.7272 mMol Now, moles of NaOH in the sample taken = 2.012-1.7272 mMol = 0.2848 mMol Therefore, exit concentration of NaOH, CA = 0.2848/10 = 0.028 M Moreover, CA0=0.1*7.5/(7.5+7.5)=0.050 M

XA = (CAO- CA)/CAO = 0.43 XA/(1-XA)2 =1.33

In this manner, and is calculated for different cases and a graph between

is plotted for each temperature to obtain the K value from its slope as discussed in the theory above.

CASE 1 T= 150C
NaO H (LPH ) 7. 5 10 .0 12 .5

ETOAc (LPH) 7.5 10.0 12. 5

(mi n) 9.07 8 5.90 0 5.41 0

Buerette Reading (ml) 17.0 16.5 17.0

NaOH consumed (mMol) 1.73 1.68 1.73

CAO (M) 0.05 0 0.050 0.050

CA (M) 0.028 0.033 0.028

XA 0.43 0.33 0.43 1.32 0.73 1.32

`Residence Time vs

Slope= 1/K

K= 9.103 CASE 2 T= 28 0C
NaO H (LPH ) 7. 5 10 .0 12 .5

= 2.197

ETOAc (mi (LPH) n) 7.5 7.5 8 5.3 10.0 3 12. 4.4 5 7

Buerette Reading (ml) 18.4 18.2 17.8

NaOH consumed (mMol) 1.81 1.86 1.83

CAO (M) 0.05 0 0.050 0.050

CA (M) 0.014 0.016 0.020

XA 0.71 0.67 0.59 8.79 6.35 3.58

Residence Time vs

10

CASE 3 T= 360C
NaO H (LPH ) 7. 5 10 .0 12 .5 ETOAc (LPH) 7.5 10.0 12. 5 (mi n) 8.5 6 5.6 4 5.1 2 Buerette Reading (ml) 18.8 18.8 18.0 NaOH consumed (mMol) 1.89 1.91 1.91

CAO (M) 0.05 0 0.050 0.050

CA (M) 0.012 0.010 0.010

XA 0.75 0.80 0.80 6 19.16 12.64 19.1

Residence Time vs

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Slope= 1.729 = 1/K

K= 11.567
T 288 299 309

-1/T -0.00347 -0.00334 -0.00324

K 9.103 10.219 11.567

Ln(K) 2.2308 2.3242 2.4481

Slope = Ea/R = 1013.8 Ea = 8428.74 Joules

RESULT
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(A)
Temperature (Kelvin) 288 299 309 9.103 10.219 11.567 Value of K

(B) Ea = 8428.74 Joules Discussion

The graph shows an increasing linear trend which is in accordance with the equation. Arrhenius eqn:

Logarithmic form:

Error analysis
1. Slope of the first graph comes out to be ve . This can be due to the following errors: Time lag in which solution was taken and the titration was conducted. So, the reaction continued and concentrations changed. Titration was erroneous. The pink solution stability and first appearance, or presence of some water in the flask. Dropper used may be of other chemical.

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